Sulfonyl cyclopentadienyl manganese tricarbonyls



United States Patent 3,290,345 SULFONYL CYCLOPENTADIENYL MANGANESETRICARBONYLS John Kozikowski, Walled Lake, Mich., and Michael Cais,

from zero to three, and Z is an alkali metal. The intermediate salt isthen reacted With an alkyl halide or an aralkyl halide which may besubstituted or unsubstituted. This process is illustrated by Way of thefollowing reac- Haifa, Israel, assignors to Ethyl Corporation, New 5tion: York, N.Y., a corporation of Virginia No Drawing. Originalapplication Aug. 12, 1960, Ser. No.

49,135. Divided and this application May 29, 1963, Rx O ZX Ser. No. SOzZSOHR/ 3 Claims. (Cl. 260-429) This application is a division ofapplication Serial No. Mnwma filed August 2 1960 now abandoried' Thls m-In the above reaction, R is an alkyl or aralkyl group, vention relatesto a variety of organometallic compounds and x is a halo en The reactionconditions em 10 ed and the processes employed in their production Moreare not critical aid the alk l or aralk lhalide whe r i u sedspecifically, this invention relates to compounds and proc- 15 y y insufficient excess, may itself serve as the solvent. The esses involvingthe use of a cyclopentadienyl sulfonic acid manganese tricarbonylcompound preparation of cyclopentadienyl sulfinioacid manganesetricarbonyls, the starting materials in this invention, and An object ofour mventlon Is to provlde new Organo' the re aration of other relatedcorn ounds is full demetallic compounds and processes for theirpreparation. p y

scribed in our copending application Serial No. 283,139, A further obect is to provide cyclopentadienyl man filed May 13 1963 now U S PatentNO 3 205 245 To 1 ;i252: ggg xfi gig ggs s s f g223:; $51 355; furtherillustrate this form of our invention, there is prefrom a reading of thespecification and claims which fol- Sented followmg genera-11 examp 1eand tables whlch 10w summarize the results obtained from several suchreac- The objects of this invention are accomplished by pre- Hons Examle 1 paring a wide variety of cyclopentadienyl manganese trip carbonylsulfone compounds. These compounds are The sodium salt derivative ofcyclopentadienyl sulfinic formed by reacting a cyclopentadienyl sulfinicacid manacid manganese tricarbonyl was dissolved in ethanol and ga ri rnyl With an alkali metal hYdTOXide Or an refluxed with a slight excessof the alkyl or aralkyl halide. alkali metal salt of an acid which isweaker than the cyclo- 0 The cooled mixture was filtered to remove thesodium pentadienyl sulfinic acid manganese tricarbonyl reactant. halidewhich formed, and the ethanolic filtrate was con- As a result, there isformed a salt having the formula centrated by heating until crystalsbegan to appear. After cooling, the crystals were collected and weregenerally SO2Z of a high degree of purity. An additional crop ofcrystals could be obtained by diluting the ethanolic mother x M )aliquor with water.

Following the general procedure set forth in the preceding example, theresults were obtained as set forth in the in which R is a univalenthydrocarbon group containing following Table I. The analyses obtainedfor the comfrom one to eight carbon atoms, x is an integer rangingpounds of Table I are set forthinTable II.

TABLE I Reflux Compound Obtained Yield, M.P. C. Recrystm R-X Time, hrs.Percent Solvent CH I 2 [(llaethylsulionyl)cyclopentadienyl] manganese 97156-158 B.

0 OlCH2l(CHa)iC]zC5HzOH 20 [(3gfiil iteia bgtyl-fihydroxybeniylsugonylg84 170-171 E.

lel'l 1113.11 8.11858 T1091 011 CHKCOCHQCl 2 c tb nfislonglycliientadienyl] y 123-124 B.

S 1 I 011 BrOH2COC5H4Mn(CO)3 3 lll gli fig igo iiydiiiangarlese)cyclopentadienyl] 94 167-168 E/B.

carbonyl methylsullonyl) cyclopentadienyl} manganese tricarbonyl.

1 B, benzene; E, ethanol. 2 3,5-di-tert-butyl-4-hydroxybenzylchloride.

3 The 2,4-dinitrophenylhydrazone of[(p-methoxyphenylsulfonyl)cyclopentadienyl] manganese tricarbonyl formedvery readily, M.P. 190-l91 (from chloroform/methanol). H, 2.60; Mn.10.9.

Analysis, Calcd. for Ci7HisMIlN40oSI C, 40.4; H, 2.57

; Mn, 10.0. Found: C, 40.5;

4 (Bromoacetylcyelopentadienyl) manganese tricarbonyl.

TABLE II Compounds Carbon Percent Hydrogen Percent Manganese PercentSulfur Percent Caled. Found Calcd. Found C alcd. Found Caled. Found Methlsulfonyl c clopentadienyl] manganese K trieazbonyl 38. 3 37. 9 2. 50 2.42 19. 4 19. 4 11.3 11. 6 [(3,5-di-tcrt-butyl-4-hydroxybenzylsulfonyl)cyclopentadienyl] manganese tricarbonyl 56. 8 56. 8 5. 63 5. 66 11.3 11.3 6. 6 6. 6 [(Acetonylsulfonyl)cyclopentadienyl] manganese tricarbonyl16. 9 16.9 l (Tricarb onylmanganese) cyclopentadienyl] carbonylmethylsulfonyl] cyclopentadienyl) manganese tricarbonyl 42. 1 42. 2 1.2. 19 21. 4 21. 5 6. 28 6. 24

I Bromoacetylcyclopentadienyl manganese tricarbonyl, which was employedas a reactant, as reported in Table I, was prepared by reacting anacylcyclopentadienyl manganese tricarbonyl compound having the formulain which R is an univalent hydrocarbon radical containing from one toabout eight carbon atoms and x is an integer ranging from zero to three,with a halogenating agent. In the specific case of the bromoacetylcompound, the halogenating agent was bromine. Analogous compounds suchas the chloroacetylcyclopentadienyl manganese tricarbonyl andiodoacetylcyclopentadienyl manganese tricarbonyl compounds are preparedby reaction of chlorine or iodine with an acetylcyclopentadienylmanganese tricarbonyl compound. The reaction can be conducted in anyinert solvent, although preferably, the sol vent is polar and mostpreferably, it is an ether. The reaction is conducted at lowtemperatures in the order of about C. To illustrate the reaction, thereis presented the following example. Example II To a solution comprising24.6 grams of acetylcyclopentadienyl manganese tricarbonyl in 250 ml. ofether cooled to 0 C. was added 16.0 grams of bromine. The bromine wasadded dropwise with stirring over a onehalf hour period. Stirring wascontinued for an additional one-half hour after which the ether andhydrogen bromide were removed by distillation of the reaction mixture atreduced pressure. The yellow-orange compound(bromoacetylcyclopentadienyl manganese tricarbonyl) which remained wasrecrystallized from ether and was found to be soluble in organicsolvents. The yield was 27 grams of bromoacetylcyclopentadienylmanganese tri carbonyl or 83 percent of theory.- The compound had amelting point of 7577 C. and on analysis there was found: C, 37.1; H,1.93; Mn, 17.0; Br, 24.8 percent. Calculated for C H MnO Br: C, 36.9; H,1.85; Mn, 16.9; Br, 24 percent.

Among the important uses of our compounds is their use as fuel and oiladditives. For example, they are useful antiknocks when added togasoline. They may be used as primary antiknocks in which they are themajor antiknock component in the fuel or as supplemental antiknocks.When used as supplemental antiknocks, they are present as the minorantiknock component in the fuel in addition to a primary antiknock suchas a tetraalkyllead compound. Typical alkyllead compounds aretetraethyllead, tetrabutyllead, tetramethyllead and'various mixed leadalkyls such as dimethyldiethyllead, diethyldibutyllead and the like.When used as either a supple mental orprimary antiknock, our compoundsmay be present in the gasoline in combination with typical scavengerssuch as ethylene dichloride, ethylene dibromide, tricresylphosphate,trimethylphosphate and the like.

The compounds of our invention have further utility as additives toresidual and distillate fuels generally, e.g., jet fuels, home heaterfuels and diesel fuels, to reduce smoke and/or soot formation. Also,they may be employed as additives to lubricating oils in which case theyact to improve the lubricity at the base oil.

Our compounds are further useful in many metal plating applications. Inorder to effect metal plating using the compounds, they are decomposedin an evacuated space containing the object to be plated. Ondecomposition, they lay down a film of metal on the object. The gaseousplating may be carried out in the presence of an inert gas so as toprevent oxidation of the plating metal or the object to be plated duringthe plating operations.

The gaseous plating technique described above finds wide application informing coatings which are not only decorative but also protect theunderlying substrate material.

Deposition of metal on a glass cloth illustrates the applied process. Aglass cloth band weighing one gram is dried for one hour in an oven atC. It is then placed in a tube which is devoid of air and there is addedto the tube 0.5 gram of [(methylsulfonyl)cyclopentadienyl] manganesetricarbonyl. The tube is heated at 400 C. for one hour after which timeit is cooled and opened. The cloth has a uniform metallic greyappearance and exhibits a gain in weight of about 0.02 gram.

A further utility for our compounds is as drying agents in which casethe compounds are incorporated in paints, varnish, printing inks,synthetic resins of the drying oil type, oil enamels and the like. Astill further utility for our compounds is their use as chemicalintermediates in the preparation of metal-containing polymeric materialsor in the preparation of new organic materials.

Having fully defined the novel compounds of our invention, their mode ofpreparation and their many utilities, we desire to be limited onlywithin the lawful scope of the appended claims.

We claim:

1. Compounds having the formula:

wherein R is a univalent hydrocarbon group containing from one to about8 carbon atoms, at is an integer ranging from 0 to 3 and R is selectedfrom the group consisting of alkyl and aralkyl groups.

2. [(Methylsulfonyl)cyclopentadienyl]manganese tricarbonyl.

3. [(3,5di-tert-butyl-4-hydroxybenzylsulfonyl)cyclopentadienyl]manganesetricarbonyl.

References Cited by the Examiner UNITED STATES PATENTS 4/ 1962 Brantley260429 OTHER REFERENCES TOBIAS E. LEVOW, Primary Examiner.

T. L. IAPALUCCI, A. DEMERS, Assistant Examiners.

1. COMPOUNDS HAVING THE FORMULA: